EP2178138A1 - Matériau actif d'électrode positive pour batterie secondaire au lithium, son procédé de fabrication, et batterie secondaire au lithium - Google Patents

Matériau actif d'électrode positive pour batterie secondaire au lithium, son procédé de fabrication, et batterie secondaire au lithium Download PDF

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EP2178138A1
EP2178138A1 EP08791482A EP08791482A EP2178138A1 EP 2178138 A1 EP2178138 A1 EP 2178138A1 EP 08791482 A EP08791482 A EP 08791482A EP 08791482 A EP08791482 A EP 08791482A EP 2178138 A1 EP2178138 A1 EP 2178138A1
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positive electrode
electrode active
active material
atoms
lithium secondary
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EP2178138B1 (fr
EP2178138A4 (fr
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Minoru Fukuchi
Hidekazu Awano
Yuuki Anbe
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Nippon Chemical Industrial Co Ltd
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Nippon Chemical Industrial Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/40—Cobaltates
    • C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/74—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by peak-intensities or a ratio thereof only
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a positive electrode active material for lithium secondary batteries, a method for producing the same, and particularly to a lithium secondary battery excellent in cycle characteristics and safety.
  • lithium-ion secondary batteries have been put in practical use as a power source of small electronic equipment such as laptop personal computers, cellular phones, and video cameras.
  • the lithium-ion secondary battery it has been reported by Mizushima et al. in 1980 ("Material Research Bulletin" vol.15, P.783-789 (1980 )) that lithium cobaltate is useful as a positive electrode active material of a lithium-ion secondary battery. Since then, extensive research and development on a lithium-based composite oxide has been carried out, and a number of proposals have been made.
  • Lithium cobaltate has been studied from the earliest days as the positive electrode materials for lithium secondary batteries because it is relatively easily synthesized and has excellent electrical properties.
  • lithium cobaltate has a drawback that raw material cobalt (Co) is rare and expensive, and it is not suitable for the increase of capacity because if it is charged with 0.7 electron or more, the crystallinity will be reduced and the electrolyte solution will be decomposed.
  • LiNiO 2 is advantageous in that it is less expensive than cobalt, it has been considered to have poorer capacitance characteristics than a Co-based material because it is liable to produce a defect and thereby reduce battery stability while in use as a positive electrode material for batteries.
  • LiNiO 2 which is close to the stoichiometric ratio as much as possible, a lithium composite oxide in which a part of nickel (Ni) is replaced with another transition metal, and a synthetic method thereof have been studied (for example, refer to Patent Documents 1 and 2).
  • LiNiO 2 and a lithium composite oxide in which a part of nickel (Ni) is replaced with another transition metal are liable to undergo gelation when kneaded with a binder resin, which causes a problem in kneading or coating properties. This is probably caused by a large amount of residual Li sources as an alkali source.
  • Patent Documents 3 and 4 The present applicants have proposed to subject the surface of LiNi x Co y Mn 2 O 2 particles to fluorination treatment (the following Patent Documents 3 and 4) to solve the above problems.
  • the present inventors have intensively studied to further improve gelation and coating properties at the time of mixing a Ni-based lithium composite oxide with a binder resin, and have found the following and completed the present invention:
  • the positive electrode active material containing Ca atoms of the present invention can be produced by a method comprising: mixing a compound containing nickel, cobalt, a transition metal atom other than these and the like with a lithium compound and a calcium compound; and firing the resulting mixture, wherein a specific calcium compound is used and the amount of the calcium compound added is defined in a specific range.
  • the positive electrode active material thus produced contains Ca atoms on the surface of the particles thereof, has a diffraction peak of CaO derived from the Ca atoms when the positive electrode active material is analyzed by X-ray diffraction, and has a reduced amount of residual Li 2 CO 3 as a Li source. Further, a lithium secondary battery using the positive electrode active material is particularly excellent in cycle characteristics and safety.
  • a positive electrode active material for lithium secondary batteries comprising a nickel-based lithium composite oxide which suppresses gelation when kneaded with a binder resin in producing a positive electrode material and provides excellent coating properties, and to provide a method for producing the same.
  • a first aspect of the present invention provides a positive electrode active material for lithium secondary batteries characterized by comprising a lithium composite oxide represented by the following general formula (1):
  • a second aspect of the present invention provides a method for producing a positive electrode active material for lithium secondary batteries, the method comprising mixing a compound containing nickel, cobalt, and Me (wherein Me represents a metal element having an atomic number of 11 or more other than Co and Ni) with a lithium compound and a calcium compound and firing the resulting mixture to produce a positive electrode active material containing a Ca atom, characterized in that one or more calcium compounds selected from the group consisting of calcium phosphate, calcium hydroxide, calcium hydrogen phosphate, calcium carbonate, calcium hypophosphite, and calcium phosphite are used as the calcium compound; and the amount of the calcium compound added is determined in the range of from 0.001 to 0.05 in terms of the molar ratio (Ca/M) of Ca atoms in the calcium compound to the total amount (M) of Ni atoms, Co atoms, and Me atoms in the compound containing the nickel, cobalt, and Me atoms.
  • Me represents a metal element having an
  • a third aspect of the present invention provides a lithium secondary battery, characterized by using a positive electrode active material for lithium secondary batteries of the first aspect of the present invention.
  • the positive electrode active material for lithium secondary batteries according to the present invention is characterized by comprising a lithium composite oxide represented by the following general formula (1):
  • the positive electrode active material for lithium secondary batteries of the present invention having the above described constitution suppresses gelation when kneaded with a binder resin in producing a positive electrode material and provides excellent coating properties, and can also impart particularly excellent cycle characteristics and safety to the lithium secondary battery using this positive electrode active material.
  • Ni atoms can be irreversibly replaced with Ca atoms by a production method to be described.
  • Me in the formula of the lithium composite oxide represented by the general formula (1) in which Ca atoms is contained represents a metal element having an atomic number of 11 or more other than Co and Ni.
  • Preferred metal elements include one or more selected from among Mn, Al, Mg, Ti, Fe, and Zr.
  • Mn atoms and/or Al atoms are particularly preferred as Me atoms in terms of improving safety of lithium secondary batteries.
  • x in general formula (1) is in the range of 0.98 ⁇ x ⁇ 1.20, and particularly preferably in the range of 1.0 or more and 1.1 or less because the initial discharge capacity of lithium secondary batteries tends to be high.
  • y in the formula is in the range of 0 ⁇ y ⁇ 0.5, and is particularly preferably in the range of more than 0 and 0.4 or less in terms of the safety of lithium secondary batteries.
  • z in the formula is in the range of 0 ⁇ z ⁇ 0.5, and particularly preferably in the range of more than 0 and 0.4 or less because the initial discharge capacity of lithium secondary batteries tends to be high.
  • the positive electrode active material containing Ca atoms of the present invention has an important constitutional feature as follows:
  • the intensity ratio (b/a) of the diffraction peaks in the range as described above in the positive electrode active material of the present invention, the amount of residual Li 2 CO 3 can be reduced, and the lithium secondary battery using this positive electrode active material has high initial discharge capacity and excellent cycle characteristics.
  • the intensity ratio (b/a) of the diffraction peaks exceeds 150, the resulting lithium secondary battery will not have sufficient cycle characteristics, and if the intensity ratio (b/a) is less than 10, the resulting lithium secondary battery will not have sufficient initial discharge capacity.
  • the content of Ca atoms is from 0.04 to 2.1% by weight, preferably from 0.4 to 1.3% by weight. This is because there is a tendency that if the content of Ca atoms is less than 0.04% by weight, the resulting lithium secondary battery will not have sufficient cycle characteristics, and on the other hand, if the content of Ca atoms exceeds 2.1% by weight, the resulting lithium secondary battery will not have sufficient initial discharge capacity.
  • the positive electrode active material containing Ca atoms be produced by mixing a compound containing nickel, cobalt, and Me atoms with a lithium compound and a calcium compound and firing the resulting mixture, because the content of Li 2 CO 3 which is produced from a Li source by a reaction and remains in the positive electrode active material can be reduced, and in particular the lithium secondary battery using this positive electrode active material has improved cycle characteristics and safety.
  • the amount of Li 2 CO 3 remaining in the positive electrode active material is preferably reduced as much as possible because it causes generation of gas in the battery in use.
  • the positive electrode active material of the present invention preferably has an amount of free anions of 1.0% by weight or less, preferably 0.5% by weight or less. This is because there is a tendency that, if the amount of free anions exceeds 1.0% by weight, a trouble such as increase in viscosity will occur when synthesizing a positive plate.
  • these free anions are derived from a calcium compound used as a raw material. Examples of the anions include phosphate ions, phosphite ions, and hypophosphite ions.
  • the positive electrode active material according to the present invention has an average particle size determined by a laser particle size distribution measurement method of from 1 to 30 ⁇ m, preferably from 5 to 25 ⁇ m. It is preferred that the average particle size be within these ranges because this allows a coating film having a uniform thickness to be formed.
  • the positive electrode active material preferably has an average particle size of from 7 to 15 ⁇ m because the lithium secondary battery using this positive electrode active material has a balanced performance from the viewpoint of cycle characteristics and safety.
  • the positive electrode active material according to the present invention has a BET specific surface area of from 0.05 to 2 m 2 /g, preferably from 0.15 to 1.0 m 2 /g.
  • the BET specific surface area is preferably within these ranges because a lithium secondary battery using this positive electrode active material is excellent in safety.
  • the method for producing the positive electrode active material for lithium secondary batteries of the present invention is a method comprising mixing a compound containing nickel, cobalt, and Me with a lithium compound and a calcium compound and firing the resulting mixture to produce a positive electrode active material containing Ca atoms, characterized in that one or more calcium compounds selected from the group consisting of calcium phosphate, calcium hydroxide, calcium hydrogen phosphate, calcium carbonate, calcium hypophosphite, and calcium phosphite are used as the calcium compound; and the amount of the calcium compound added is determined in the range of from 0.001 to 0.05 in terms of the molar ratio (Ca/M) of Ca atoms in the calcium compound to the total amount (M) of Ni atoms, Co atoms, and Me atoms in the compound containing the nickel, cobalt, and Me atoms.
  • Examples of the compound containing nickel, cobalt, and Me atoms preferably used as the first raw material preferably include a composite hydroxide, a composite oxyhydroxide, a composite carbonate, and a composite oxide.
  • the composite hydroxide can be prepared, for example, with a coprecipitation method.
  • the composite oxide can be coprecipitated by mixing an aqueous solution containing nickel, cobalt, and Me atoms, an aqueous solution of a complexing agent, and an aqueous alkali solution (refer to Japanese Patent Laid Open No. 10-81521 , Japanese Patent Laid Open No. 10-81520 , Japanese Patent Laid Open No. 10-29820 , and Japanese Patent Laid Open No.
  • the composite oxyhydroxide can be obtained by yielding a precipitate of the composite hydroxide according to the above-described coprecipitation operation followed by blowing air into the reaction mixture to oxidize the composite oxide.
  • the composite oxide can be obtained by yielding a precipitate of the composite hydroxide according to the above-described coprecipitation operation followed by heat-treating the precipitate, for example, at 200 to 500°C.
  • the composite carbonate can be obtained by preparing the aqueous solution containing nickel, cobalt, and Me atoms and the aqueous solution of a complexing agent in the same manner as in the above-described coprecipitation operation and mixing the resulting aqueous solutions with the aqueous alkali solution as an aqueous solution of alkali carbonate or alkali hydrogen carbonate.
  • the compound containing nickel, cobalt, and Me atoms have an average particle size as determined by a laser light scattering method of from 1 to 30.0 ⁇ m, preferably from 5.0 to 25.0 ⁇ m because such a compound has good reactivity.
  • the preferred composition of the compound containing nickel, cobalt, and Me atoms is the molar ratio of y and z in the formula of the lithium composite oxide represented by general formula (1) as described above.
  • the compound containing nickel, cobalt, and Me atoms may be a commercially available product.
  • lithium compound used as the second raw material examples include an oxide, a hydroxide, a carbonate, a nitrate, and an organic acid salt of lithium.
  • lithium hydroxide is particularly preferably used from the viewpoint of its reactivity with the compound containing nickel, cobalt, and Me atoms used as the first raw material. It is particularly preferred that the lithium compound have an average particle size as determined by a laser light scattering method of from 1 to 100 ⁇ m, preferably from 5 to 80 ⁇ m because such a compound has good reactivity.
  • the calcium compound used as the third raw material is a component for reducing the residual Li 2 CO 3 in the positive electrode active material of the present invention.
  • the calcium compound comprises calcium phosphate, calcium hydroxide, calcium hydrogen phosphate, calcium carbonate, calcium hypophosphite, and calcium phosphite.
  • calcium phosphate and calcium hydroxide are preferred in that these compounds are highly effective in reducing the amount of residual Li 2 CO 3 and can impart excellent cycle characteristics and safety to the lithium secondary batteries using the positive electrode active material of the present invention.
  • the physical properties and the like of the calcium compound is not limited, but it is particularly preferred that the calcium compound have an average particle size as determined by a laser light scattering method of from 1 to 30 ⁇ m, preferably from 5 to 10 ⁇ m because such a compound has good reactivity and is significantly effective in reducing the amount of residual Li 2 CO 3 .
  • the compound containing nickel, cobalt, and Me atoms, the lithium compound, and the calcium compound used as the first to third raw materials, respectively preferably have an impurity content as low as possible in order to produce a high purity positive electrode active material.
  • the positive electrode active material for lithium secondary batteries of the present invention can be obtained by firing a mixture comprising the compound containing nickel, cobalt, and Me atoms as the first raw material, the lithium compound as the second raw material, and the calcium compound as the third raw material so that the amount of the calcium compound added is determined in a specific range.
  • the compound containing nickel, cobalt, and Me atoms as the first raw material, the lithium compound as the second raw material, and the calcium compound as the third raw material are mixed in a predetermined ratio.
  • the mixing may be a dry process or a wet process, but a dry process is preferred because production is simple. In the case of dry blending, it is preferable to use a blender or the like so that raw materials are uniformly mixed.
  • the blending ratio of the first raw material and the third raw material is determined so that the ratio of calcium atoms (Ca) in the calcium compound as the third raw material to the total amount (M) of nickel, cobalt, and Me atoms in the compound containing nickel, cobalt, and Me atoms as the first raw material is in the range of from 0.001 to 0.05, preferably from 0.005 to 0.03 in terms of the molar ratio (Ca/M).
  • the amount of residual Li 2 CO 3 is reduced to 0.5% by weight or less, preferably to 0.4% by weight or less, most preferably to 0.3% by weight or less by determining the amount of Ca atoms blended in the above-described range.
  • the resulting lithium secondary battery using such a positive electrode active material is particularly excellent in cycle characteristics and safety.
  • the molar ratio (Ca/M) of Ca atoms is less than 0.001, the resulting lithium secondary battery will not have good cycle characteristics, and if the molar ratio (Ca/M) of Ca atoms exceeds 0.05, the resulting lithium secondary battery will have a reduced initial discharge capacity. Therefore, these molar ratios are not preferred.
  • the ratio of lithium atoms (Li) in the lithium compound as the second raw material to the total amount (M) of nickel, cobalt, and Me atoms in the compound containing nickel, cobalt, and Me atoms as the first raw material is preferably determined in the range of from 0.98 to 1.2, preferably from 1.0 to 1.1 in terms of the molar ratio (Li/M).
  • the resulting lithium secondary battery using such a positive electrode active material has high discharge capacity and is excellent in cycle characteristics by determining the amount of Li atoms blended in the above-described range.
  • the resulting lithium secondary battery tends to show a rapid reduction in the initial discharge capacity, and if the molar ratio of Li atoms exceeds 1.2, the resulting lithium secondary battery tends to have a reduced cycle characteristics. Therefore, these molar ratios are not preferred.
  • a mixture in which the raw materials are uniformly mixed is fired.
  • a mixture which produces water it is preferable to fire the mixture in the air or in an oxygen environment by multistage firing.
  • the mixture is slowly fired at a temperature range of about 200 to 400°C where moisture contained in the raw materials disappears and then rapidly heated to a temperature range of 700 to 900°C followed by being fired for 1 to 30 hours.
  • the firing may be performed any number of times as needed.
  • a fired mixture is ground, and then the ground fired mixture may be fired again for the purpose of obtaining uniform powder characteristics.
  • the mixture is fired and then appropriately cooled, and the cooled mixture is ground as needed to obtain the positive electrode active material of the present invention.
  • the grinding performed as needed is appropriately performed when the positive electrode active material obtained by firing is a weakly combined block like material, and the particle of the positive electrode active material itself has the following specific average particle size and specific BET specific surface area.
  • the resulting positive electrode active material containing Ca has an average particle size of from 1 to 30 ⁇ m, preferably from 5 to 25 ⁇ m, and a BET specific surface area of from 0.05 to 2.0 m 2 /g, preferably from 0.15 to 1.0 m 2 /g.
  • the positive electrode active material of the present invention obtained in this way has the above powder characteristics.
  • the lithium secondary battery according to the present invention uses the above positive electrode active material for lithium secondary batteries and comprises a positive electrode, a negative electrode, a separator, and a nonaqueous electrolyte containing a lithium salt.
  • the positive electrode is formed, for example, by coating and drying a positive electrode mixture on a positive electrode current collector.
  • the positive electrode mixture comprises a positive electrode active material as described above, a conducting agent, a binder, and a filler to be added as needed.
  • the lithium secondary battery according to the present invention has a positive electrode on which the positive electrode active material as described above is uniformly applied. Therefore, the lithium secondary battery according to the present invention hardly causes reduction in load characteristics and cycle characteristics.
  • the content of the positive electrode active material in the positive electrode mixture is from 70 to 100% by weight, preferably 90 to 98% by weight.
  • the positive electrode current collector is not particularly limited as long as it is an electronic conductor which does not cause a chemical change in a constituted battery.
  • Examples of the positive electrode current collector include stainless steel, nickel, aluminum, titanium, baked carbon, and those prepared by surface-treating the surface of aluminum or stainless steel with carbon, nickel, titanium, or silver. These materials may be used in the state where the surface thereof is oxidized, or may be used in the state where the surface of the current collector is imparted with unevenness by surface treatment.
  • Examples of the form of the current collector include foil, film, sheet, net, punched product, lath body, porous material, foam, fiber, and molded product of nonwoven fabric.
  • the thickness of the current collector is not particularly limited, and is preferably in the range of from 1 to 500 ⁇ m.
  • the conducting agent is not particularly limited as long as it is an electronic conducting material which does not cause a chemical change in a constituted battery.
  • the conducting agent include graphite such as natural graphite and artificial graphite, carbon blacks such as carbon black, acetylene black, Ketchen black, channel black, furnace black, lamp black, and thermal black, conductive fibers such as carbon fiber and metal fiber, metal powders such as carbon fluoride, aluminum, and nickel powder, conductive whiskers such as zinc oxide and potassium titanate, conductive metal oxide such as titanium oxide, and conductive materials such as a polyphenylene derivative.
  • the natural graphite include flaky graphite, scaly graphite, and earthy graphite. These can be used independently or in combination of two or more.
  • the compounding ratio of the conducting agent in the positive electrode mixture is from 1 to 50% by weight, preferably from 2 to 30% by weight.
  • binder examples include polysaccharide, thermoplastic resins, and polymers having rubber elasticity such as starch, polyvinylidene fluoride, polyvinyl alcohol, carboxymethylcellulose, hydroxypropylcellulose, regenerated cellulose, diacetyl cellulose, polyvinyl pyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, an ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, styrene butadiene rubber, fluororubber, a tetrafluoroethylene-hexafluoroethylene copolymer, a tetrafluoroethylene-hexafluoropropylene copolymer, a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, a vinylidene fluoride-hexafluoropropylene copolymer, a vinylidene fluoride-chlor
  • the compounding ratio of the binder in the positive electrode mixture is from 1 to 50% by weight, preferably from 5 to 15% by weight.
  • the filler suppresses the volume expansion of the positive electrode in the positive electrode mixture, and is added as needed.
  • Any filler can be used as long as it is a fibrous material which does not cause a chemical change in a constituted battery.
  • the filler to be used include fibers of an olefinic polymer such as polypropylene and polyethylene, glass, carbon, and the like.
  • the amount of the filler to be added is not particularly limited, and is preferably from 0 to 30% by weight in the positive electrode mixture.
  • the negative electrode is formed by coating and drying a negative electrode material on a negative electrode current collector.
  • the negative electrode current collector is not particularly limited as long as it is an electronic conductor which does not cause a chemical change in a constituted battery.
  • Examples of the negative electrode current collector include stainless steel, nickel, copper, titanium, aluminum, baked carbon, those prepared by surface-treating the surface of copper or stainless steel with carbon, nickel, titanium, or silver, and an aluminum-cadmium alloy. Further, these materials may be used in the state where the surface thereof is oxidized, or may be used in the state where the surface of the current collector is imparted with unevenness by surface treatment.
  • Examples of the form of the current collector include foil, film, sheet, net, punched product, lath body, porous material, foam, fiber, and molded product of nonwoven fabric.
  • the thickness of the current collector is, but is not particularly limited, preferably in the range of from 1 to 500 ⁇ m.
  • Examples of the negative electrode material include, but are not particularly limited to, a carbonaceous material, a metal composite oxide, a lithium metal, a lithium alloy, a silicon-based alloy, a tin-based alloy, a metal oxide, a conductive polymer, a chalcogen compound, and a Li-Co-Ni-based material.
  • Examples of the carbonaceous material include a non-graphitizable carbon material and a graphite-based carbon material.
  • Examples of the metal composite oxide include compounds such as Sn p (M 1 ) 1-p (M 2 ) q O r (wherein M 1 represents one or more elements selected from Mn, Fe, Pb, and Ge; M 2 represents one or more elements selected from Al, B, P, Si, Group 1 elements, Group 2 elements, and Group 3 elements of the Periodic Table, and halogen elements; and p, q, and r are represented by the formulae 0 ⁇ p ⁇ 1, 1 ⁇ q ⁇ 3, and 1 ⁇ r ⁇ 8, respectively), Li x Fe 2 O 3 (0 ⁇ x ⁇ 1), and Li x WO 2 (0 ⁇ x ⁇ 1).
  • Examples of the metal oxide include GeO, GeO 2 , SnO, SnO 2 , PbO, PbO 2 , Pb 2 O 3 , Pb 3 O 4 , Sb 2 O 3 , Sb 2 O 4 , Sb 2 2O 5 , Bi 2 O 3 , Bi 2 O 4 , and Bi 2 O 5 .
  • Examples of the conductive polymer include polyacethylene and poly-p-phenylene.
  • the separator there is used an insulating thin film having high ion permeability and a predetermined mechanical strength.
  • An olefinic polymer such as polypropylene, or glass fiber, or a sheet or nonwoven fabric made of polyethylene or the like is used because these materials have organic solvent resistance and hydrophobicity.
  • the pore size of the separator may be generally within the range useful for batteries, and it is, for example, from 0.01 to 10 ⁇ m.
  • the thickness of the separator may be within the general range for batteries, and it is, for example, from 5 to 300 ⁇ m. Note that, when a solid electrolyte such as a polymer is used as an electrolyte to be described below, the solid electrolyte may also be used as the separator.
  • the nonaqueous electrolyte containing a lithium salt comprises a nonaqueous electrolyte and a lithium salt.
  • a nonaqueous electrolyte solution there is used a nonaqueous electrolyte solution, an organic solid electrolyte, and an inorganic solid electrolyte.
  • nonaqueous electrolyte solution examples include an aprotic organic solvent such as N-methyl-2-pyrrolidinone, propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ⁇ -butyrolactone, 1,2-dimethoxyethane, tetrahydroxyfuran, 2-methyltetrahydrofuran, dimethylsulfoxide, 1,3-dioxolane, formamide, dimethylformamide, dioxolane, acetonitrile, nitromethane, methyl formate, methyl acetate, trialkyl phosphate, trimethoxymethane, a dioxolane derivative, sulfolane, methyl sulfolane, 3-methyl-2-oxazolidinone, 1,3-dimethyl-2-imidazolidinone, a propylene carbonate derivative, a tetrahydrofuran derivative, diethyl ether, 1,3-propane
  • organic solid electrolyte examples include a polymer containing an ionic dissociation group such as a polyethylene derivative, a polyethylene oxide derivative or a polymer containing the same, a polypropylene oxide derivative or a polymer containing the same, a phosphoric ester polymer, polyphosphazene, polyaziridine, polyethylene sulfide, polyvinyl alcohol, polyvinylidene fluoride, and polyhexafluoropropylene, and a mixture of the polymer containing an ionic dissociation group and the above nonaqueous electrolyte solution.
  • an ionic dissociation group such as a polyethylene derivative, a polyethylene oxide derivative or a polymer containing the same, a polypropylene oxide derivative or a polymer containing the same, a phosphoric ester polymer, polyphosphazene, polyaziridine, polyethylene sulfide, polyvinyl alcohol, polyvinylidene fluoride, and
  • the inorganic solid electrolyte there can be used a Li nitride, a Li halide, an oxyacid salt of Li, a Li sulfide, and the like.
  • the inorganic solid electrolyte include Li 3 N, LiI, Li 5 NI 2 , Li 3 N-LiI-LiOH, LiSiO 4 , LiSiO 4 -LiI-LiOH, Li 2 SiS 3 , Li 4 SiO 4 , Li 4 SiO 4 -LiI-LiOH, P 2 S 5 , Li 2 S or Li 2 S-P 2 S 5 , Li 2 S-SiS 2 , Li 2 S-GeS 2 , Li 2 S-Ga 2 S 3 , Li 2 S-B 2 S 3 , Li 2 S-P 2 S 5 -X, Li 2 S-SiS 2 -X, Li 2 S-GeS 2 -X, Li 2 S-Ga 2 S 3 -X, Li 2 S-
  • the inorganic solid electrolyte is an amorphous material (glass)
  • the following compounds can be contained in the inorganic solid electrolyte: compounds containing oxygen such as lithium phosphate (Li 3 PO 4 ), lithium oxide (Li 2 O), lithium sulfate (Li 2 SO 4 ), phosphorus oxide (P 2 O 5 ), and lithium borate (Li 3 BO 3 ); and compounds containing nitrogen such as Li 3 PO 4-x N 2x/3 (wherein x is represented by the formula 0 ⁇ x ⁇ 4), Li 4 SiO 4-x N 2x/3 (wherein x is represented by the formula 0 ⁇ x ⁇ 4), Li 4 GeO 4-x N 2x/3 (wherein x is represented by the formula 0 ⁇ x ⁇ 4), and Li 3 BO 3-x N 2x/3 (wherein x is represented by the formula 0 ⁇ x ⁇ 3).
  • Addition of the compounds containing oxygen or the compounds containing nitrogen will increase the clearance between the amorphous
  • the lithium salt there is used a material which is dissolved in the above nonaqueous electrolyte.
  • the lithium salt include LiCl, LiBr, LiI, LiClO 4 , LiBF 4 , LiB 10 Cl 10 , LiPF 6 , LiCF 3 SO 3 , LiCF 3 CO 2 , LiAsF 6 , LiSbF 6 , LiB 10 Cl 10 , LiAlCl 4 , CH 3 SO 3 Li, CF 3 SO 3 Li, (CF 3 SO 2 ) 2 NLi, chloroborane lithium, lower aliphatic carboxylic acid lithium, 4-phenyl lithium borate, and imides, and a salt obtained by mixing two or more of the above lithium salts.
  • the following compounds can be added to the nonaqueous electrolyte in order to improve discharge and charge characteristics and flame retardancy.
  • examples include pyridine, triethyl phosphite, triethanolamine, cyclic ether, ethylenediamine, n-glyme, hexaphosphoric triamide, a nitrobenzene derivative, sulfur, a quinone-imine dye, N-substituted oxazolidinone and N,N-substituted imidazolidine, ethylene glycol dialkyl ether, an ammonium salt, polyethylene glycol, pyrrole, 2-methoxyethanol, aluminum trichloride, a monomer for a conductive polymer electrode active material, triethylene phosphonamide, trialkylphosphine, morpholine, an aryl compound having a carbonyl group, hexamethylphosphoric triamide and 4-alkyl morpholine, bicyclic tertiary amine, oil, a
  • the electrolyte solution can further contain a halogen-containing solvent such as carbon tetrachloride and ethylene trifluoride. Further, in order to improve high-temperature storage characteristics, the electrolyte solution can contain carbon dioxide gas.
  • the lithium secondary battery according to the present invention is a lithium secondary battery excellent in battery performance, particularly cycle characteristics, and the shape of the battery may be any shape, such as a button, a sheet, a cylinder, a square, and a coin type.
  • Examples of the applications of the lithium secondary battery according to the present invention include, but are not particularly limited to, electronic equipment such as notebook personal computers, laptop personal computers, pocket word processors, cellular phones, cordless phone units, portable CD players, radios, liquid crystal televisions, backup power supply, electric shavers, memory cards, and video movies, and consumer electronics for automobiles, motorized vehicles, game machines, and the like.
  • electronic equipment such as notebook personal computers, laptop personal computers, pocket word processors, cellular phones, cordless phone units, portable CD players, radios, liquid crystal televisions, backup power supply, electric shavers, memory cards, and video movies, and consumer electronics for automobiles, motorized vehicles, game machines, and the like.
  • the positive electrode active material according to the present invention can reduce the amount of residual Li 2 CO 3 as a Li source, but it is not clear how this effect is obtained. Probably, when a specific calcium compound is used and fired together with a raw material mixture, the reactivity of the lithium compound used as a raw material is improved, or the residual Li 2 CO 3 is efficiently decomposed.
  • the calcium compounds and barium compounds having various physical properties as shown in Table 2 were used as the added compounds. Note that the average particle size was determined by a laser particle size distribution measurement method.
  • Ca 3 (PO 4 ) 2 and Ca(OH) 2 there were used those manufactured by Junsei Chemical Co., Ltd.
  • BaHPO 4 and Ba(OH) 2 ⁇ 8H 2 O there were used those manufactured by Kanto Chemical Co., Inc.
  • a composite hydroxide containing nickel, cobalt, and manganese atoms shown in Table 3, lithium hydroxide monohydrate (average particle size; 74 ⁇ m), and the above calcium phosphate were mixed in an amount as shown in Table 3 and sufficiently dry-blended to obtain a homogeneous mixture of these raw materials. Subsequently, the mixture was heated to 300°C in 1 hour, maintained at this temperature for 2 hours, heated to 850°C in 5 hours, and maintained at this temperature for 7 hours, followed by firing the resulting mixture in the air. A fired material obtained by completing the firing and then cooling the fired mixture was ground and classified to obtain a positive electrode active material comprising Li 1.03 Ni 0.8 Co 0.1 Mn 0.1 O 2 and Ca atoms contained therein.
  • positive electrode active materials to which calcium phosphate is not added were prepared as Comparative Examples 1, 4, and 5.
  • a composite hydroxide containing nickel, cobalt, and manganese atoms shown in Table 3, lithium hydroxide monohydrate (average particle size; 74 ⁇ m), and the above calcium hydroxide were mixed in an amount as shown in Table 3 and sufficiently dry-blended to obtain a homogeneous mixture of these raw materials. Subsequently, the mixture was heated to 300°C in 1 hour, maintained at this temperature for 2 hours, heated to 850°C in 5 hours, and maintained at this temperature for 7 hours, followed by firing the resulting mixture in the air. A fired material obtained by completing the firing and then cooling the fired mixture was ground and classified to obtain a positive electrode active material comprising Li 1.03 Ni 0.8 Co 0.1 Mn 0.1 O 2 and Ca atoms contained therein.
  • a composite hydroxide containing nickel, cobalt, and manganese atoms shown in Table 4, lithium hydroxide monohydrate (average particle size; 74 ⁇ m), and a barium hydroxide as described above were mixed in an amount as shown in Table 3 and sufficiently dry-blended to obtain a homogeneous mixture of these raw materials. Subsequently, the mixture was heated to 300°C in 1 hour, maintained at this temperature for 2 hours, heated to 850°C in 5 hours, and maintained at this temperature for 7 hours, followed by firing the resulting mixture in the air. A fired material obtained by completing the firing and then cooling the fired mixture was ground and classified to obtain a positive electrode active material comprising Li 1.03 Ni 0.8 Co 0.1 Mn 0.1 O 2 and Ba atoms contained therein.
  • the above composite hydroxide containing nickel, cobalt, and aluminum atoms, lithium hydroxide monohydrate (average particle size; 74 ⁇ m), and the above calcium hydroxide were mixed in an amount as shown in Table 5 and sufficiently dry-blended to obtain a homogeneous mixture of these raw materials. Subsequently, the mixture was heated to 300°C in 1 hour, maintained at this temperature for 2 hours, heated to 850°C in 5 hours, and maintained at this temperature for 7 hours, followed by firing the resulting mixture in the air. A fired material obtained by completing the firing and then cooling the fired mixture was ground and classified to obtain a positive electrode active material comprising Li 1.01 Ni 0.82 Co 0.15 Al 0.03 O 2 and Ca atoms contained therein.
  • the average particle size was determined by a laser particle size distribution measurement method, and the results are shown in Table 6.
  • the residual Li 2 CO 3 content was measured as described below.
  • the X-ray diffraction pattern of the positive electrode active material obtained in Example 3 is shown in Figure 1 .
  • the intensity ratio (b/a) is 42.
  • the Ca content was determined by ICP-atomic emission spectrometry.
  • a positive electrode agent was prepared by mixing 91% by weight of a lithium-transition metal composite oxide obtained in any one of Examples 1 to 10 and Comparative Examples 1 to 9, 6% by weight of graphite powder, and 3% by weight of polyvinylidene fluoride, and the resulting positive electrode agent was dispersed in N-methyl-2-pyrrolidinone to prepare a kneaded paste. This kneaded paste was applied to aluminum foil, dried, and punched into a disk with a diameter of 15 mm by pressing to obtain a positive plate.
  • a lithium secondary battery was manufactured by using this positive plate and using members such as a separator, a negative electrode, a positive electrode, a current collector plate, fittings, an external terminal, and an electrolyte solution.
  • members such as a separator, a negative electrode, a positive electrode, a current collector plate, fittings, an external terminal, and an electrolyte solution.
  • metal lithium foil was used as the negative electrode
  • electrolyte solution there was used a solution prepared by dissolving 1 mol of LiPF6 in 1 liter of a 1:1 kneaded liquid of ethylene carbonate and methylethyl carbonate.
  • the manufactured lithium secondary battery was operated under the following conditions at room temperature to evaluate the following battery performance.
  • the positive electrode was subjected to charge and discharge, one cycle of the charge and discharge including operations of charging the positive electrode to 4.3 V over 5 hours at 1.0 C with a constant-current constant-voltage (CCCV) charge, followed by discharging the charged electrode to 2.7 V at a discharge rate of 0.2 C.
  • the discharge capacity was measured for every cycle.
  • the above cycle was repeated 20 times, and the capacity maintenance rate was calculated by the following formula from the discharge capacity at the first cycle and the 20th cycle. Note that the discharge capacity at the first cycle is referred to as the initial discharge capacity.
  • Table 7 The results are shown in Table 7.
  • Capacity maintenance rate % discharge capacity at the 20 ⁇ th cycle / discharge capacity at the first cycle ⁇ 100
  • a positive electrode agent was prepared by mixing 91% by weight of a lithium-transition metal composite oxide obtained in any one of Examples 1 to 10 and Comparative Examples 1 to 7, 6% by weight of graphite powder, and 3% by weight of polyvinylidene fluoride, and the resulting positive electrode agent was dispersed in N-methyl-2-pyrrolidinone to prepare a kneaded paste. Ten grams of the resulting mixed paste was dropped on the upper part of a glass plate (40 cm in width ⁇ 50cm in length) inclined at 45 degrees, and the fluidity used as an index of gelation was evaluated along with the following. The results are shown together in Table 7.
  • the positive electrode active material of the present invention is excellent in coating stability, has an initial discharge of 160 (mAH/g) or more which is a practical level, and has a capacity maintenance rate of 90% or more, indicating that this positive electrode active material is excellent also in cycle characteristics.
  • the positive electrode active materials in Comparative Examples 1 and 2 and Comparative Examples 4 to 9 have poor coating stability; and the positive electrode active material in Comparative Example 3 is excellent in coating stability but has a capacity maintenance rate of less than 90%, indicating that it has a problem in cycle characteristics.
  • the positive electrode active material according to the present invention comprising a nickel-based lithium composite oxide suppresses gelation when kneaded with a binder resin in producing a positive electrode material and provides excellent coating properties. Therefore, the use of the positive electrode active material according to the present invention provides a lithium secondary battery excellent in cycle characteristics and safety due to reduction in generation of gas from the battery in use.

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EP4101945B1 (fr) 2021-06-09 2024-05-15 Epinovatech AB Dispositif pour effectuer une électrolyse de l'eau et système associé
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